Compounds of the Alkali and Alkaline Earth Metals in Organic Synthesis

Wakefield, B. J.

doi:10.1016/b978-008046518-0.00090-8

Cited by 12 publications

(2 citation statements)

References 650 publications

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“…The Grignard reaction has been undoubtedly one of the most powerful and useful reactions for the formation of C-C bonds since its discovery over 100 years ago. [22][23][24] The intrinsically highly polarized C-Mg bond present in the Grignard reagent is endowed with strong nucleophilicity towards nucleophilic addition. However, this inherent attribute also limits its practical applications owing to the issues associated with the stringent anhydrous conditions as well as functional group compatibility.…”

Section: Grignard-type Reactions In Watermentioning

confidence: 99%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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Chemistry has always had as a target the conversion of molecules into valuable materials. Nevertheless, the aim of past synthesis has primarily focused on achieving a given transformation, regardless of the environmental impact of the synthetic route. Given the current global situation, the demand for sustainable alternatives has substantially increased. Our group focuses on developing selective chemical transformations that benefit from mild conditions, improved atom economy, and that can make use of renewable feedstocks as starting materials. This account summarizes our work over the past two decades specifically regarding the selective removal, conversion, and addition of functional groups that can, later on, be applied at a late stage for the modification of complex molecules.

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Section: Grignard-type Reactions In Watermentioning

confidence: 99%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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“…I t is widely recognized that the Barbier-Grignard-type reaction is one of the most important methods for forming carboncarbon bonds and has widespread synthetic applications in modern organic chemistry [1][2][3][4] . Conventionally, successful handling of these reactions necessitates the strict control of anhydrous conditions, which imposes limitations on synthetic design 5 .…”

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confidence: 99%

The Barbier–Grignard-type arylation of aldehydes using unactivated aryl iodides in water

Zhou

2014

Nat Commun

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Carbon-carbon bond formation is the essence of organic synthesis. One of the most important methods for forming carbon-carbon bonds is the Barbier-Grignard-type reaction, which was discovered over a century ago. However, it is still highly desirable to further improve this process. In this article, we describe a Barbier-Grignard-type direct arylation of aldehydes by using unactivated iodides mediated by zinc and catalysed by rhodium in water. This method bypasses a number of challenges encountered by the conventional BarbierGrignard reaction, such as strict exclusion of moisture and air, protection-deprotection of various acidic hydrogens in the substrates, and so forth. It thereby creates a safer, more convenient and more environmentally benign strategy to access the diarylmethanols and aryl alkyl alcohols, ubiquitous skeletons found in fine chemicals, biologically active molecules and pharmaceuticals. Importantly, the same reaction performed in an organic solvent proceeded sluggishly to give much inferior yields.

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Beryllium & Magnesium: Organometallic ChemistryBased in part on the article Beryllium & Magnesium: Organometallic Chemistry by E. Alexander Hill which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Saulys

Hill

2005

Encyclopedia of Inorganic Chemistry

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Victor Grignard found in 1900 that solutions of organomagnesium halides form easily in the reaction of an organic halide with magnesium metal in diethyl ether. These Grignard reagents undergo useful reactions with many kinds of substrates. This discovery ushered in a new era in organometallic chemistry and provided chemists with a powerful and versatile reagent for synthesis of a wide variety of organic and organometallic compounds. This article discusses Grignard reagents in the broader context of organomagnesium chemistry. Preparatory methods surveyed include direct reaction of organic halides with the metal, exchange reactions with other organometallic compounds, as well as carbo‐ and hydrometalations. The current level of understanding of the mechanism of Grignard formation is summarized. The formation and reactivity of unusual species such as cluster Grignard reagents, for example, RMg 4 X (R = organic group, and X = halide) and polymagnesium compounds, for example, Ru[C 5 (MgCl) 5 ] 2 are also discussed. The bonding and structure of organomagnesium compounds (as well as that of beryllium analogues) as described by diffraction methods, thermochemical data, colligative properties, spectroscopic (vibrational, nuclear magnetic, and electronic) measurements, kinetic studies, mass spectrometry, and theoretical methods are outlined. The most prominent chemical property of organomagnesium compounds is their ability to deliver an effectively ‘anionic’ organic group with nucleophilic properties. As alkylating reagents, their important reactions include nucleophilic displacement of less basic leaving groups from saturated carbon atoms or other elements, addition to carbonyl groups and other unsaturated functions, and nucleophilic substitution at the acyl group of carboxylic acid derivatives. This broad array of substrates is surveyed, as are the effects of solvents and catalysts on reactivity. Less conspicuous reactions with wholly or predominantly inorganic substrates are also considered. Electron transfer reactions where organomagnesium compounds act as reductants are discussed. Organoberyllium compounds are more difficult to prepare and are less nucleophilic than their magnesium counterparts. These features, together with their high toxicity, have limited their utility. Methods of preparation, as well as descriptions of bonding, structure, and reactivity patterns are presented. Of special note are recent advances in cyclopentadienyl beryllium chemistry, as well as the advent of beryllium–silicon chemistry.

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Compounds of the Alkali and Alkaline Earth Metals in Organic Synthesis

Cited by 12 publications

References 650 publications

Exploration of new reaction tools for late-stage functionalization of complex chemicals

Exploration of new reaction tools for late-stage functionalization of complex chemicals

The Barbier–Grignard-type arylation of aldehydes using unactivated aryl iodides in water

Beryllium & Magnesium: Organometallic ChemistryBased in part on the article Beryllium & Magnesium: Organometallic Chemistry by E. Alexander Hill which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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